On the relevance of iron adsorption to container materials in small-volume experiments on iron marine chemistry: Fe-aided assessment of capacity, affinity and kinetics

Iron chemistry in seawater has been extensively studied in the laboratory, mostly in small-volume sample bottles. However, little has been reported about iron wall sorption in these bottles. In this paper, radio-iron ⁵⁵Fe was used to assess iron wall adsorption, both in terms of capacity, affinity and kinetics. Various bottle materials were tested. Iron sorption increased from polyethylene/polycarbonate to polymethylmetacrylate (PMMA)/high-density polyethylene/polytetrafluoroethylene to glass/quartz, reaching equilibrium in a 25–70 h period. PMMA was studied in more detail: ferric iron (Fe(III)) adsorbed on the walls of the bottles, whereas ferrous iron (Fe(II)) did not. Considering that in seawater the inorganic iron pool mostly consists of ferric iron, the wall will be a factor that needs to be considered in bottle experiments.The present data indicate that for PMMA with specific surface (S)-to-volume (V) ratio S/V, both iron capacity (42 ± 16 × 10^− 9 mol/m² or 1.7 × 10^− 9 mol/L recalculated for the S/V-specific PMMA bottles used) and affinity (log K_Fe'W = 11.0 ± 0.3 m²/mol or 12.4 ± 0.3 L/mol, recalculated for the S/V-specific PMMA bottles used) are of similar magnitude as the iron capacity and -affinity of the natural ligands in the presently used seawater and thus cannot be ignored.Calculation of rate constants for association and dissociation of both Fe'L (iron bound to natural occurring organic ligands) and Fe'W (iron adsorbed on the wall of vessels) suggests that the two iron complexes are also of rather similar kinetics, with rate constants for dissociation in the order of 10 ⁻⁴–10^− 5 L/s and rate constants for association in the order of 10⁸ L/(mol s). This makes that iron wall sorption should be seriously considered in small-volume experiments, both in assessments of shorter-term dynamics and in end-point observations in equilibrium conditions. Therefore, the present data strongly advocate making use of iron mass balances throughout in experiments in smaller volume set-ups on marine iron (bio) chemistry.     

Dissociation constants of protonated methionine species in seawater media

The dissociation constants (pK₁ and pK₂) for methionine have been measured in artificial seawater as a function of salinity (S = 5 to 35) and temperature (5 to 45 °C). The seawater pK₂ values were lower than the values in NaCl at the same ionic strength while the pK₁ values in seawater were lower only at S = 35. In an attempt to understand these differences, we have made measurements of the constants in Na–Mg–Cl solutions at 25 °C. The measured values have been used to determine the formation of Mg²⁺ complexes and Pitzer interaction parameters for Mg²⁺ with methionine. The seawater model with the interaction parameters accounts for the differences between the value of pK₁ and pK₂ between NaCl and seawater. This study demonstrates that it is important to consider all of the ionic interactions in natural waters when examining the dissociation of organic acids.     

Geochemical dissociation of major and trace elements in bed and suspended sediment phases of the phosphate mines effluent water, Jordan

The bed and suspended (slime) sediment phases associated with effluent water that are produced from phosphate-ore-upgrading process at Al-Abyad mine in the southern part of Jordan were analyzed chemically and mineralogically. The results show that the effluent water is highly oxic and mildly alkaline in nature. The geochemical behavior of each phase was controlled by the effluent water physicochemical parameters, sediment particle size, mineralogical constituents of the studied phases, and the prevailing climatic nature of the area. Bed sediments have higher concentrations of many elements than slime. Accordingly, the bed sediments can be considered as a sink rather than a pool for many elements. The geochemical dissociation of major oxides and trace elements between bed and slime sediments was evident using t test, particularly between P₂O₅, SiO₂, CaO, K₂O, Mn, Sr, Y, and Co, and to lesser extent, V, U, Zn, and Cr. This might be attributed to effluent water characteristics, mineralogy, and the presence of fine-grained materials. The spatial distribution of major oxide and trace element concentrations along the stream drainage exhibited a slight increase with distance either in bed or slime sediment phases. However, they increased suddenly at the last three sampling sites, which might be due to the abundance of fine-grained materials that are mainly composed of clay minerals (montmorillonite) that would enhance the adsorption process. Moreover, the XRD results confirmed the existence of elemental geochemical dissociation as a function of mineral control.     

Submarine slope stability analysis during natural gas hydrate dissociation

ABSTRACT

The purpose of this paper is to analyze the stability of submarine slope during the natural gas hydrate dissociation. A model is deduced to calculate the excess pore fluid pressure. In addition, a new method is proposed to define and calculate the factor of safety (FoS) of the submarine slope. Case study is also performed, results of which show that dissociation of hydrates would decrease the stability of submarine slope. If the cohesion of the hydrate-bearing sediments is small, the submarine slope would become unstable because of the shear failure. If the cohesion of the hydrate-bearing sediments is large enough, the tensile failure would happen in the hydrate-bearing sediments and the excess pore pressure may explode the submarine slope. Under the drained condition, the submarine slope may remain stable because the buildup of excess pore fluid pressure could not take place. Moreover, FoS would be underestimated by the assumption that natural gas hydrates dissociate in the horizontally confined space, but would be overestimated by only taking into account of the base of the natural gas hydrate-bearing sediments. The compressibility factor of natural gas should also be considered because treating natural gas as ideal gas would underestimate the stability of submarine slope.     

Examination of core samples from the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope: Effects of retrieval and preservation

Collecting and preserving undamaged core samples containing gas hydrates from depth is difficult because of the pressure and temperature changes encountered upon retrieval. Hydrate-bearing core samples were collected at the BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well in February 2007. Coring was performed while using a custom oil-based drilling mud, and the cores were retrieved by a wireline. The samples were characterized and subsampled at the surface under ambient winter arctic conditions. Samples thought to be hydrate bearing were preserved either by immersion in liquid nitrogen (LN), or by storage under methane pressure at ambient arctic conditions, and later depressurized and immersed in LN. Eleven core samples from hydrate-bearing zones were scanned using x-ray computed tomography to examine core structure and homogeneity. Features observed include radial fractures, spalling-type fractures, and reduced density near the periphery. These features were induced during sample collection, handling, and preservation. Isotopic analysis of the methane from hydrate in an initially LN-preserved core and a pressure-preserved core indicate that secondary hydrate formation occurred throughout the pressurized core, whereas none occurred in the LN-preserved core, however no hydrate was found near the periphery of the LN-preserved core. To replicate some aspects of the preservation methods, natural and laboratory-made saturated porous media samples were frozen in a variety of ways, with radial fractures observed in some LN-frozen sands, and needle-like ice crystals forming in slowly frozen clay-rich sediments. Suggestions for hydrate-bearing core preservation are presented.     

298.15K下LiCl-Li_2B_4O_7-H_2O体系中LiCl的活度系数和离解平衡研究

用锂离子选择电极和经典 Ag- Ag Cl电极测定了 2 98.15K下 L i Cl- Li2 B4 O7- H2 O体系中离子强度范围为 0 .0 1～ 2 .50 mol· kg-1,不同 Li2 B4 O7离子强度分数的 L i Cl的平均活度系数。由实验数据 ,用迭代法及多元线性回归法 ,求取了 L i2 B4 O7的化学计量离解平衡常数 Km,热力学离解平衡常数 K及 Pitzer离子作用参数 ,并与实验值比较标准偏差为 0 .0 50 0。同时该实验结果在 0 .0 1- 0 .50 mol·kg-1离子强度范围内与 2 98.15K下 L i Cl- L i2 SO4 - H2 O体系 L i Cl平均活度系数的变化趋势进行了比较 ,得到 L i Cl在 Li2 B4 O7介质中平均活度系数随 Yb的增大而增大 ,而在 L i2 SO4 介质中则减小     

Methane-derived authigenic carbonates from the northern Gulf of Mexico — MD02 Cruise

Authigenic carbonates were sampled in piston cores collected from both the Tunica Mound and the Mississippi Canyon area on the continental slope of the northern Gulf of Mexico during a Marion Dufresne cruise in July 2002. The carbonates are present as hardgrounds, porous crusts, concretions or nodules and shell fragments with or without carbonate cements. Carbonates occurred at gas venting sites which are likely to overlie gas hydrates bearing sediments. Electron microprobe, X-ray diffraction (XRD) and thinsection investigations show that these carbonates are high-Mg calcite (6–21 mol% MgCO₃), with significant presence of framboidal pyrite. All carbonates are depleted in ¹³C (δ¹³C = − 61.9 to − 31.5‰ PDB) indicating that the carbon is derived mainly from anaerobic methane oxidation (AMO). Age estimates based on ¹⁴C dating of shell fragments and on regional sedimentation rates indicate that these authigenic carbonates formed within the last 1000 yr in the Mississippi Canyon and within 5500 yr at the Tunica Mound. The oxygen isotopic composition of carbonates ranges from + 3.4 to + 5.9‰ PDB. Oxygen isotopic compositions and Mg²⁺ contents of carbonates, and present in-situ temperatures of bottom seawater/sediments, show that some of these carbonates, especially from a core associated with underlying massive gas hydrates precipitated in or near equilibrium with bottom-water. On the other hand, those carbonates more enriched in ¹⁸O are interpreted to have precipitated from ¹⁸O-rich fluids which are thought to have been derived from the dissociation of gas hydrates. The dissociation of gas hydrates in the northern Gulf of Mexico within the last 5500 yr may be caused by nearby salt movement and related brines.     

Effects of dissociation on the shear strength and deformation behavior of methane hydrate-bearing sediments

A series of tests were conducted in order to investigate the shear strength and deformation behavior of methane hydrate-bearing sediments during dissociation using the thermal recovery method or depressurization method. An innovative temperature-controlled high pressure triaxial apparatus which can reproduce the in situ conditions of hydrate reservoirs was used. The results indicate that: (1) the failure strength of isotropically consolidated methane hydrate-bearing sediments which dissociated completely using the thermal recovery method is less than that of pure Toyoura sand. However, the initial stiffness and volumetric strain are higher than that of pure Toyoura sand. (2) The thermal recovery method will cause the failure of methane hydrate-bearing sediments when the axial load is higher than the strength of methane hydrate-bearing sediments after dissociation. (3) The depressurization method will not cause collapse of methane hydrate-bearing sediments during depressurization. However, water pressure recovery will lead to failure when the axial load is larger than the strength of the methane hydrate-bearing sediments after dissociation. (4) The depressurization rate shows little effect on the ultimate deformation of methane hydrate-bearing sediments, while the initial deformation rate increases with increasing depressurization rate. (5) The larger the reduction of pore pressure, the larger axial strain and volumetric strain.     

南海北部神狐海域天然气水合物分解的测井异常

南海北部神狐海域GMGS-1钻探揭示SH3井天然气水合物位于稳定带上部,厚度约为10 m.氯离子异常计算的水合物饱和度最高达26%,高水合物饱和度层出现高电阻率和低纵波速度.为分析该低纵波速度异常,本文基于简化的三相介质理论计算了饱和水纵波速度,在深度195 m附近,测量的纵波速度小于饱和水纵波速度.利用阿尔奇公式,基于原位温度、盐度、密度孔隙度和测量的电阻率,利用交会分析确定了该井的阿尔奇常数为a=1.1和m=2.3.基于该参数,利用阿尔奇方程计算的水合物饱和度占孔隙空间5%~20%,局部地层水合物饱和度达26.8%,在垂向上分布不均匀.由于钻探可能导致水合物发生分解而产生游离气,原位游离气和水合物分解产生的气体都能造成低纵波速度异常.由于地震资料采集在测井之前完成,利用不同速度制作合成地震记录并与地震资料进行对比,能够确定水合物稳定带上部的低速异常形成原因.